MIP工艺及其专用催化剂的工业应用

抚顺石化分公司石油二厂1．5Mt／a催化裂化装置于2010年12月进行MIP—CGP工艺改造,并于2011年12月使用专用催化剂CGP—FS。应用结果表明,当CGP—FS催化剂占系统藏量75％时,与使用降烯烃催化剂LDO-70时相比,汽油辛烷值RON上升3．5个单位,达到90左右;汽油烯烃保持在32％左有;液化气丙烯含量上升13％;柴油变重、密度增加、十六烷值下降到22．5;油浆变重、密度增加,芳香烃含量达到85％左右;液化气收率增加5．33％,汽油产率下降2．62％,油浆产率下降2．27％,轻收下降2．89％,总液收上升1．44％。     

甲醇制清洁油品催化剂级配工艺研究

介绍甲醇制汽油催化剂级配技术。通过不同酸中心数量和酸强度分布的催化剂级配实验发现,与单一类型催化剂相比,采用级配装填方式可以使催化剂性能互补,单程汽油收率大于70%;在保证甲醇完全转化情况下,改变气体产物分布,进一步提高目标产品收率,催化反应所得汽油中的芳烃含量降低,异构烷烃含量增加,改善了油品质量。     

热解条件对西湾煤与秸秆流化床加压共热解的影响

在流化床加压热解装置中考察温度、压力、气氛和生物质掺混比等条件对西湾煤与秸秆共热解特性的影响,结果表明:在600℃,0.3 MPa,100%N₂气氛条件下,随着生物质掺混比增加,共热解油产率先增加后降低,实验值均大于计算值;当生物质掺混比为30%(质量分数)时,共热解油的实验值达到最大(16.90%),高于计算值(13.05%);热解压力由常压升至1.0 MPa时,受高氢分压作用下较多的氢分子参与自由基的加氢饱和作用,共热解油产率先增加后降低,在0.3 MPa时共热解油产率达到最大(17.90%);100%(体积分数,下同)N₂,100%CO₂和50%CO₂+50%H₂气氛下的共热解油产率分别为16.73%,16.55%和16.07%;与焦油相比,共热解油的密度变化不大,在元素中碳的质量分数由79.32%降低至71.80%,硫的质量分数由0.60%降低至0.31%,n(H)/n(C)增加;共热解油中脂肪烃、芳香烃和含氧化合物的质量分数降低,酚类组分的质量分数增加,三环及以上的多环产物裂解为小分子化合物,油品质量得到改善。     

Four-lump kinetic model for fluid catalytic cracking process

In the fluid catalytic cracking reactor heavy gas oil is cracked into more valuable lighter hydrocarbon products. The reactor input is a mixture of hydrocarbons which makes the reaction kinetics very complicated due to the involved reactions. In this paper, a four-lump model is proposed to describe the process. This model is different from others mainly in that the deposition rate of coke on catalyst can be predicted from gas oil conversion and isolated from the C₁–C₄ gas yield. This is important since coke supplies heat required for endothermic reactions occurring in the reactor. By this model we can also conclude that the C1–C4 gas yield increases with increasing reactor temperature, while production of gasoline and coke decreases.     

Fluid catalytic cracking feed hydrotreatment and its severity impact on product yields and quality

This paper investigates the effect of fluid catalytic cracking (FCC) feed hydrotreatment and its severity increase on product yields and quality obtained in a commercial and a laboratory MAT FCC units. The hydrotreatment of Ural heavy vacuum gas oil reduces not only sulfur, nitrogen, Conradson carbon and metals content in the FCC feed but also increases the mononuclear aromatic hydrocarbons content by 8% absolute at almost no change in the total aromatics content. Regardless of this 8% increase of the mononuclear aromatics in the hydrotreated FCC feed the conversion increase in both commercial and laboratory MAT units was only 2%. The severity increase in the FCC feed hydrotreater leads to a higher conversion in the FCC, higher hydrogen transfer rate that results in higher isobutane/butylenes ratio, lower gasoline olefins content, and higher gasoline motor octane number. The hydrotreatment of the Ural heavy vacuum gas oil exhibited the same changes in FCC catalyst selectivities: lower coke and LCO selectivities and higher gasoline selectivity in both commercial riser FCC unit that has between 2 and 3 s time on stream, and the fixed bed reactor MAT unit, that has 30 s time on stream.     

Catalytic cracking of rapeseed oil to high octane gasoline and olefins

Rapeseed is the most important energy crop in Europe. The basic idea of the presented work was to add vegetable oils to the standard FCC-feed in order to meet requirements on the increasing demand for climate-friendly produced fuels. The experimental test program was conducted in a fully continuously operated FCC pilot plant with internal CFB-design at Vienna University of Technology. Rapeseed oil was added in steps of 20 m% to the conventional feedstock, up to 100 m% addition. The influence on the process was observed. The obtained product spectrum at 550 °C was slightly modified in relation to standard feed VGO. The gasoline yield stayed roughly constant while the crack-gas yield decreased at higher ratios of rapeseed oil. Due to the oxygen content of rapeseed oil the additional lumps water and CO₂ are formed. Using pure rapeseed oil as feedstock for FCC leads to a total fuel yield on total feed of approximately 65 m% (23 m% gaseous hydrocarbons plus 42 m% gasoline). The gasoline achieved is oxygen free at high octane numbers of approximately RON 100 and MON 86.     

顺序输送混油规律的数值模拟

基于CFD中多相流（VOF）模型,采用有限体积法,建立了重油前轻油后及重油后轻油前顺序输送}昆油模型。以柴油和汽油为例,分别在0°、30°、45°、60°及90° 5种管道倾角情况下进行了数值模拟。研究表明：柴油前行,随着倾角的增加,混油带逐渐增加;汽油前行,随着倾角的增加,混油带逐渐缩短;柴油前行的混油带大于汽油前行的混油带;实际生产中,对于不同倾角管道顺序输送宜采用轻油在前、重油在后的顺序。     

催化汽油和C4烃类在LBO-A催化剂上芳构化反应的实验研究

在小型固定流化床实验装置上，单独利用催化裂化提高辛烷值助剂LBO-A为催化剂，分别对催化汽油和C₄烃类进行了催化转化反应的实验研究，考察了反应温度和空速对反应产物分布和组成的影响。实验结果表明，LBO-A单独作为催化剂对催化汽油和C₄烃类具有较强的芳构化性能，同时，所产裂化气体中，丙烯含量远高于普通裂化催化剂。因此，在适宜的反应条件下，可生产高辛烷值的汽油组分，同时，增产丙烯，并且这两种性能随反应温度的升高而增强。     

热分解气氛对流化床煤热解制油的影响

在循环流化床锅炉上耦合流化床热解反应器既可提供电力又副产热解油,明显提高煤的利用价值。在这个过程中,热解反应器通常利用自身产生的热解气作为流化介质。本文考察了模拟热解气反应气氛对流化床煤热解拔头制取热解油产率的影响,并利用TG-FTIR分析了焦油官能团组成及随TG温度的变化。针对锅炉用烟煤的实验结果表明：采用热解气作为反应气氛时焦油产率最大,相对无水无灰基煤达13%。反应气氛中H₂和CO₂的存在不利于焦油生成,但CO 和CH₄的加入提高了焦油产率;H₂的加入有利于焦油中酚羟基、羧基类化合物生成,同时也促进了脂肪族化合物的裂解;CH₄的存在可以提高焦油中单环芳烃、脂肪族及酚羟基类化合物的含量。     

国内外清洁汽油技术进展

对比了欧洲和我国的清洁汽油质量指标，分析了发达国家清洁汽油硫含量变化情况。对国内外清洁汽油的技术进展情况进行了综述，建议在碳五碳六异构化技术、固体超强酸烷基化技术、汽柴油清净分散剂等等技术上进行深入研发，以利我国的清洁汽油技术的快速发展。     

新型CDCM催化剂在两段提升管催化裂化装置上的应用

CDCM催化剂在800 kt·a^－1两段提升管重油催化裂化装置（TSRFCC）上的应用结果表明,该催化剂具有活性高、目的产品选择性好、重油裂解能力强和抗重金属污染能力强的特点。能显著改善产品分布和提高产品质量，在操作条件基本不变的情况下，液态烃收率和总液收分别可提高2.80和0.60个百分点，同时汽油辛烷值和诱导期提高，液态烃中丙烯含量增加。     

Fuels by pyrolysis of waste plastics from agricultural and packaging sectors in a pilot scale reactor

The pyrolysis of waste plastics (so called chemical recycling) is one perspective way of their utilizations, but the end product properties are a key point of the industrial leading of processes. In this paper a pilot scale pyrolysis process has been investigated. Waste plastics were decomposed in a tube reactor at 520 °C, using hourly feed rate of 9.0 kg. Raw materials were selectively collected wastes from agricultural and packaging industry. For supporting the more intensive cracking of CC bonds of main polymer structure a commercial ZSM-5 catalyst was tested in concentration of 5.0%. Products were separated into gases, gasoline, light and heavy oil by distillation. Plastic wastes could be converted into gasoline and light oil with yields of 20–48% and 17–36% depending on the used parameters. The gas and liquid products had significant content of unsaturated hydrocarbons, principally olefins. In the presence of ZSM-5 catalyst the yields of lighter fractions (especially gasoline) could be considerably increased and the average molecular weight of each fraction has decreased. Gasoline had C₅–C₁₅ hydrocarbons, while light oil had C₁₂–C₂₈. The used catalyst has promoted the formation of i-butane in gases and affected the composition of both gasoline and light oil. Properties of products are advantageous for fuel-like applications, and they are able to increase the productivity of refinery. On the other hand the possibility for further utilization of products from pyrolysis basically was affected by the source and the properties of raw materials. Waste polyethylene from agricultural consisted of some elements from fertilizers (N, S, P and Ca), which could not be removed from the surfaces of raw materials by pre-treatment (e.g. washing). In that case significant concentration of N, S, P and Ca can be measured in all products, but the catalyst has decreased the concentration of impurities. Gasoline, light oil and heavy oil were nitrogen free and sulphur content was below 12 mg/kg in hydrocarbons obtained by the pyrolysis of polypropylene waste from packaging.     

Effect of Sulfur on the Fischer-Tropsch Synthesis

One of the principalcauses of present concern is the current unavailability of alternative sources of fuels for transporation. Other fuel imensive sectors, such as electric power generation, can depend on coal or nuclear fuel to provide the energy if petroleum-based fuels become scare. The transporation sector, on the other hand, is projected to need liquid fuels. Due to the relevant abundance of coal in the United States, it isimperative to find ways of converting coal to liquid fuels. Products from coal liquefaction processes contain a high aromatic content. Though this is a desirable comporent isgasoline, it is a very undersirable one in jet and diesel fuels (Table 1). In even higher boiling materials such as gas oils, the high aromatic content makes it quite difficult to produce gasoline by normal rednery processess. Fischer-Tropsch (FT)synthesis, in which carbon produces mainly straight chain aliphatic hydrogen obtained from coal gastfication are reacted over a caralyst, is the only develped coal-derived process which produces mainly straight chain aliphatic hydrocarbons. Although such aliphatic hydrocarbons are not very desirable on motor gasolines due to their low octare number, diesel and jet fuels containing such aliphatic, hydrocarbons are considered high quality materials. In addition, the higher boiling gas oil traction from the FT process is easily converted to gasoline and diesel fuel by conventional refining technology     

Catalytic conversion of palm oil to fuels and chemicals

The conversion of palm oil to hydrocarbons using a shape selective zeolite catalyst is reported in this work. Palm oil was passed over HZSM-5 catalyst in a fixed bed micro-reactor and the reactor was operated at atmospheric pressure, a temperature range of 360 to 420°C and weight hourly space velocity (WHSV) of 2 to 4 h^?1. The main objective was to study the effect of reaction temperature and oil space velocity on the conversion and selectivity of gasoline range hydrocarbons. The results show that 40 to 70wt% of the palm oil can be converted to aromatics and hydrocarbons in the gasoline, diesel and kerosene range, light gases, coke and water. The maximum gasoline range hydrocarbons yield of 40wt% of total product formed was obtained at 400°C and 2 h^?1 space velocity.     

微乳化含水乙醇汽油及其乳化剂最佳HLB值研究

实验研究了油、乙醇、水三者含量对含水乙醇汽油体系的影响关系,探讨含水乙醇汽油的相分离机理,应用微乳化理论优选和复配乳化剂,研究含水乙醇汽油乳化剂的最佳HLB值及乙醇含量、水含量对含水乙醇汽油乳化剂最佳HLB值的影响关系。试验结果表明：混合燃料的稳定性随水含最增加而下降,随乙醇含量的增加而上升;含水乙醇汽油乳化剂的最佳HLB值在5．5～6．5之间;且含水乙醇汽油乳化剂的最佳HLB值随水含量的增加有降低的趋势,受乙醇含量的影响不显著。     

Catalytic conversion of canola oil to fuels and chemical feedstocks Part I. Effect of process conditions on the performance of HZSM-5 catalyst

The conversion of canola oil to hydrocarbons using a shape selective zeolite catalyst is reported in this work. Canola oil was passed over HZSM-5 catalyst in a fixed bed micro-reactor and the effects of reaction temperature and oil space velocity on the conversion and selectivity were studied using a statistical experimental design. The results show that 60–95 wt% of the canola oil can be converted to hydrocarbons in the gasoline boiling range, light gases and water. The gasoline fraction contained 60–70 wt% of aromatic hydrocarbons and the gases were mostly C₃ and C₄ paraffins. Furthermore, the spent catalyst could be regenerated completely at 600°C in 1 h with dry air.     

重油催化裂解汽柴油二次裂解性能研究

This paper investigated the secondary cracking of gasoline and diesel from the catalytic pyrolysis of Daqing atmospheric residue on catalyst CEP-1 in a fluidized bed reactor.The results show that the secondary cracking reactivity of gasoline and diesel is poor,and the yield of total light olefins is only about 10%（by mass）.As reaction temperature increases,ethylene yield increases,butylene yield decreases,and propylene yield shows a maximum.The optimal reaction temperature is about 670℃for the production of light olefins.With the enhance- ment of catalyst-to-oil mass ratio and steam-to-oil mass ratio,the yields of light olefins increase to some extent. About 6.30%of the mass of total aromatic rings is converted by secondary cracking,indicating that aromatic hy- drocarbons are not easy to undergo ring-opening reactions under the present experimental conditions.     

乙烯装置裂解气分馏及冷却的模拟计算

对于含有众多复什碳氢化合物的裂解汽油、裂解柴油和裂解燃料油等宽馏分以及氢、轻烃、大量水分的裂解气，采用虚拟组分以减少组分总数、用惰性气体描述水在烃类中的相行为，以物流混合和闪蒸过程组成一个闪蒸平衡级，并以逐级闪蒸计算来描述乙烯装置的裂解气分馏塔。     

混合废塑料裂解液相产物的分析

通过SH/T 0558色谱模拟蒸馏技术和成分检测分析混合废塑料裂解得到的液相产物。详细介绍了SH/T 0558色谱模拟蒸馏技术快速测定裂解油馏程的方法,采用nC_9、nC_(10)混合物作为裂解油模拟蒸馏的内标物,使用常规峰面积归一分析方法,经过处理产生色谱模拟蒸馏的测定报告。该方法样品用量少,操作简便,分析速度快,结果精确,最大相对标准偏差为0.75%,能够较好的模拟裂解油馏程。混合废塑料热裂解和催化裂解得到的液相产物中汽油和柴油的含量较高,油品质量较好。对混合废塑料热裂解和催化裂解所获得的两种油样进行饱和烃、芳烃和烯烃成分检测,有催化剂参与后烯烃+芳烃的总量为85.2%,其汽油辛烷值很高,可作为高标号优质汽油组分。     

LAP-2降低FCC汽油烯烃含量助剂的工业应用

沧州石化公司炼油厂FCC汽油烯烃体积分数一直维持在45％～50％。对其FCC装置进行了LAP-2助剂降烯烃工业试验，结果表明，当LAP-2在FCC装置维持藏量5％时，FCC汽油烯烃体积分数可降低12％，并增产丙烯，汽油辛烷值维持不变。